Dyestuffs of the urea-azine series and process of preparing the same



Patented May 24, 1932 UNITED stares nearest caries WILLIAM ARTHURSILVESTER, or BLACKLEY, airmcrmsrnn, nnerann, .assreivonro :snrrrsnnyns'rurrs CORPORATION LIMITED, or MANCHESTER, ENGLAND DYESTUFFS OF THEUREA-AZINE SERIES AND PEQCESS IREPARING THE SAME 1% Drawing. Applicationfiled m 16, 1928, Serial No. 278,340, and in Great Britain June 7, 1927.

This invention relates to a new series of dyes capable of dyeing cottondirectly and applicable also to the dyeing of regenerated cellulosematerials.

It is well known that simple sulphonated aminoazo compounds may beconverted by phosgenation into direct cotton dyes (see, for

example, Colour Index, Nos. 347, 348 and 349 I have now discovered thatby the action of phosgene upon certain acid wool dyes, other than azodyes, containing a free amino or mono substituted amino group, underconditions to be described, compounds of the urea type are formed whichhave good direct wherein R represents hydrogen of a substituent groupand R represents a sulphona-ts which containstwo or more sulphonicgroups and wherein R and R represent alkyl, aryl ed a'z'ine nucleus ofthe type which contains two or more sulphonic groups urea nucleus by acarbon atom which is ex- 4 ternal to the azine ring system. Thesecomplex urea dyes are dark colored powders and dye wool, cotton andregenerated cellulose in a very advantageous manner. These products maybe obtained by the action of phosgene preferably in the presence of anacid- ,7

binding agent, upon suitably chosen acid wool dyes of the azine series;or, alternatively, they may be synthesized from suitable v ,cleus-of thetype ureas by the usual reactions for the formation of azlnes. Thus wemay start with a sulpl-io nated azine acid wool dye of the type:

which contains two or more sulphonic groups and wherein R and Rrepresent alkyl, aryl or aralkyl groups andR represents a monovalentaryl residue. A compound of this structure possesses little, or nodirect aliinity for cotton or, for regenerated cellulose. By

phosgenation in the presence ofanalkali it is converted into a ureahaving the probable structure R-lG O-ld-R wherein R represents asulphonated azine nucleus of the type or aralkyl groups and R representsa-monovalent aryl nucleus. i Under the broad class of dyes of thepresent invention I find that the subclass of dyes wherein thesulphonated azinenucleus contains three sulphonic groups are especiallyadvantageous. This subclass may berepr'esented by the probable generalformula wherein R represents' a sulphonated azine nuwhich contains threesulphonic groups and wherein R represents an alkyl group, R representsalkyl or aralkyl groups, R represents a divalent aryl nucleus and Rrepresents a monovalent aryl nucleus. These complex ureas are darkcolored powders soluble in water to blue to violet solutions, sparinglysoluble in alcohol, regenerating, by prolonged hydrolysis with alkalies,acid wool colors of the azine series containing a diazotizable aminogroup. These complex urea dyes have aflinity for W001, cotton andregenerated cel lulose materials and produce blue shades upon thesematerials, the exact shade varying with the specific sulphonated azinenucleus present in the complex urea.

Other azine acid wool dyes, in which the amino group or mono-substitutedamino group is situated in other parts of the molecule, may also be usedas parent materials for phosgenation. c

My invention is illustrated, but not limited by the following example,in which the parts are by weight. V

E mampZe.Ten parts of the acid wool dyestuff of the formula:

SOaH

' (see German Patent No. 193,472, Examples 1 and 3), are dissolved, assodium salt, in

' 200300 parts of water. is passed into the solution and at the sameCarbonyl chloride time aqueous sodium hydroxide is added in suiiicientquantity to keep the solution weakly The introduction of carsodiumhydroxide solution with the chemically. equivalent amount of carbonylchloride are needed. The product is salted out 7 and dried in the usualway. In the form of its sodium salt, the urea is a bronzy, dark bluepowder, giving in water at a dilution of 1: 3000 a violet solution andat greater concentrations, (such as 1: 500) a blue solution,

av blue solution being also obtained at the" higher dilutions byaddition of sodium chloride, the said urea giving in concentratedsulphuric acid a bright green solution becoming blue on'dilution withseparation of a blue fiocculent precipitate, the said urea'dyeingfcotton and regenerated cellulose materials in bright blue'shades, andwool in somewhat redder blue shades.

Amongst other acid azine dyes'which I' have found to give similarresults are those having the following formulae:

SOxH

SQaH I 7 their conversion into my. new products takes placequite'smoothly as described in the example given above.

For the production of, the most valuable products according to myinvention, I start with an azine dye containing three sulphonic groups,which may be disposed in any convenient positions in the molecule, 7

What I claim and desire to'secure by Letters Patent is i v 1. In themanufacture of new complex urea. dyes suitable for dyeing cotton'andregenera-ted cellulose, the process which comprises treating withphosgene a sulphonated azine acid wool dye having an azine nucleus T7?of the type which contains. three sulphonic groups and wherein Rrepresents a benzene nucleus, R represents a benzene nucleus, Rrepresents an alkyl group andR representsanalkyl o re...

aralkyl' group. p H r I r 2. In the manufactureof new complex urea dyessuitable 'for dyeing cotton and regenerated,,cel-lulose, the processwhich comprises These dyes all made by the general .me't'hod of GermanPatent No. 193,472, and 1 treating with phos'gene a 'sulphonated azinewool dyeliaving anazine nucleus of the type which. contains threesulphonic groups and wherein R represents an alkyl group and Rrepresents an alkyl or aralkyl group.

3. In the manufacture of new complex urea dyes suitable for dyeingcotton and regenerated cellulose, the process which comprises treatingwith phosgene a sulphonated azine acid wool dye having an azine nucleusof the type wherein R represents an alkyl group.

4. In the manufacture-of new complex urea dyes suitable for dyeingcotton and regenerated cellulose, the process which comprises treatingwith phosgene a sulphonated azine acid wool dye having an azine nucleusof the type SQaH ) ence of sodium hydroxide.

7. its new articles of manufacture, the

complex urea dyes having the probable general formula 11 H R'1 1"O-I IRg wherein R represents a sulphonated azine nucleus of the type whichcontains" three. sulph'onic groups and in which the H p p v I I-'andN-=7 groups are attached to R in the para position with respect to eachother, and wherein R represents a benzene nucleus, R5 represents abenzene nucleus, R represents an alkyl group, R represents an alkyl oraralkyl group and X represents hydrogen, an alkyl or sulphonic group,the said complex urea dyes being dark colored powders and dyeing wool,cotton and regenerated cellulose in blue shades. p

8. As new articles of manufacture, (10mplex urea dyes havin the probablegeneral formula it W r i g H i 7 sn pe-1 :42

a; wherein R represents a sulphonated azine nucleus of the type SOmH . Ued;

which contains three sulphonic groups and wherein R represents an alkylgroup and R represents an alkyl or aralkyl group, the said'cellulose'inblue shades.

9. As new articles of manufacture, complex urea dyes having the probablegeneral wherein R represents sulphonated azine nucleus of the typewherein R represents an alkyl group, the said complex urea dyes beingdark colored powders and dyeing wool, cotton and regenerated cellulosein blue shades.

10. As new articles of manufacture, com plex ureadyes having theprobable general formula i V RJI i I ilN/ll c wherein R represents asulphonated "azine formula:

nucleus of the type the said complex urea dyes being bronzy,

dark blue powders and dyeing cotton and regenerated cellulose materialsin bright blue shades and wool in somewhat redder blue shades.

V 11. As new articles of manufacture, complex urea dyes having theprobable general H I n R-fI-o-fI-n wherein R represents a sulphonatedazine nucleus of the typev wherein R represents an alkyl group andrepresents H or. SO H' being dark colored owd-ers and dyeing wool,cotton and regenerated cellulose bright greenish blue shades.

12. As new articles of manufacture, complexurea dyes having the probablegeneral formula:

wherein'R represents a 'sulphonated azine nucleus of the type c H018 VRe N= N N Rl Hols 7 7 wherein R rrepresents an alkyl group, said complexurea dyes being dark colored powders and dyeing wool, cotton andregenerated cellulose bright greenish blue shades.

13. As new articles of manufacture, complex urea dyes" having theprobable general formulai ai al,

wherein R represents a sulphonated azine nucleus'of the type HOaS I /OH3N- N I a orn Hogs SOaH

said complex urea, dyes being dark colored powders and dyeing wool,cotton and regenerated cellulose in blue shades.

14:. As new articles of manufacture, complex urea dyes having theprobable general formula:

wherein R represents a sulphonated azine nu plex urea 'dyes having theprobable general formula:

H H V RI T--OI IR wherein R represents a sulphonated azine nucleus ofthe type" 7 Rs O, N 1103f I 7 H2 l tog soin wherein R 'represents an'alkyl group.

16. As new articles of manufacture, complex urea dyes having theprobable general formula wherein R represents a sulphonated azinenucleus of the type C2116 @NJ I L4 @0111 I H l sou-1 said complex ureadyes being dark powders and dyeing W001, cotton and regeneratedcellulose in blue shades.

In testimony whereof I a-fl iX my signature. WILLIAM ARTHUR SILVESTER.

CERTIFICATE .OF 4 CORRECTION.

Patent No. 1,859,477. May 24, 1932.

WILLIAM ARTHUR SILVESTER.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,line 27, for the word "of" read or; and that the said Letters Patentshould be read with this correction therein that the same may conform tothe record of the case in the Patent Office.

Signed and sealed this 12th day of July, A. D. 1932.

M. J. Moore,

(Seal) Acting Commissioner of Patents.

